Water treatment compositions and methods of use

ABSTRACT

Methods for clarifying water, reducing turbidity of water, and removing phosphate from water include adding a water treatment composition having an aluminum-containing coagulant, and a natural non-charged polysaccharide, such as guar. The aluminum-containing compound can include polyaluminum chloride, aluminum chlorohydrate, polyaluminum chlorohydrate, aluminum sulfate, sodium aluminate, polyaluminum sulfate, polyaluminum silicate chloride, polyaluminum silicate sulfate, or a combination thereof.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/851826, filed Mar. 27, 2013, which claims the benefit of U.S.Provisional Application No. 61/798333, filed on Mar. 15, 2013, and U.S.Provisional Application No. 61/616943, filed on Mar. 28, 2012, all ofwhich are herein expressly incorporated by reference.

BACKGROUND

The removal of suspended matter from water is a concern for municipalwater treatment plants, industrial water treatment plants, environmentalstorm water, and recreational water. Coagulation and flocculation arewell known processes for the removal of suspended matter. Coagulationmay be viewed as the initial process of destabilizing or neutralizingcharges on suspended particles so that they begin to aggregate.Coagulation is usually combined with flocculation, sedimentation, orfiltration. Flocculation is the aggregation of the particles into largermasses. There are presently many chemicals on the market that assistwith coagulation and/or flocculation. Among these are the metal salts,such as polyaluminum chlorides, aluminum sulfate, ferric sulfate, andferric chloride. Cationic polymers, such as chitosan, may also be usedas coagulants. Chitosan is a polymer derived from naturally occurringchitin. Chitin is a linear polysaccharide composed of α-(1-4)-linked2-acetoamido-2-deoxy-D-glucose units that occur naturally in theexoskeleton of invertebrates, in particular, the carapace of marinecrustaceans. Chemical deacetylation of chitin yields chitosan, which isa copolymer of 2-amino-2-deoxy-D-glucose and2-acetoamido-2-deoxy-D-glucose units.

While it is known that water turbidity can be reduced using metallicsalts, it is generally desirable to reduce the overall amount ofmetallic salts used, while maintaining the desired water clarity.Accordingly, new ways of using metallic salts are constantly beingsought.

SUMMARY

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This summary is not intended to identify key features ofthe claimed subject matter, nor is it intended to be used as an aid indetermining the scope of the claimed subject matter.

Some embodiments are related to a composition that is used forclarifying and reducing the turbidity of water by treating the waterwith a water treatment composition comprised of guar and polyaluminumchloride or aluminum chlorohydrate or polyaluminum chlorohydrate oraluminum sulfate or sodium aluminate or polyaluminum sulfate orpolyaluminum silicate chloride or polyaluminum silicate sulfate, or acombination thereof so as to cause the agglomeration and subsequentremoval of shear-stable insoluble suspended and/or partiallywater-soluble flocs and aggregates by collection on or within a filtermedia that allows easier more efficient backwashing and improvedprolonged use of said filter media. The method comprises adding aneffective amount of the water treatment composition to the watercontaining insoluble suspended and/or partially water soluble dissolvedmaterial and allowing the water treatment composition to interact withthe suspended insoluble or soluble matter in order to allow the matterto agglomerate and settle under gravity and/or float to the surface. Theagglomerated matter can be separated from the water by any of a numberof means known in the art such as filtration, gravity settling,centrifugation, cyclone separator, vacuum filtration, or by flotationand skimming.

The water treatment composition can be comprised of a liquid solutioncontaining an aluminum-containing compound such as polyaluminumchloride, aluminum chlorohydrate, polyaluminum chlorohydrate, aluminumsulfate, sodium aluminate, polyaluminum sulfate, polyaluminum silicatechloride, polyaluminum silicate sulfate, or a combination thereof and awater-soluble natural non-chemically derivatized polysaccharide(s)derived from a plant, microbe, or animal.

An exemplary embodiment of the water treatment composition comprises thepolysaccharide guar and polyaluminum chloride.

Another exemplary embodiment of the water treatment compositioncomprises guar and aluminum sulfate.

Another exemplary embodiment of the water treatment compositioncomprises guar and aluminum chlorohydrate.

Another exemplary embodiment of the water treatment compositioncomprises guar and polyaluminum chlorohydrate.

Another exemplary embodiment of the water treatment compositioncomprises guar and sodium aluminate.

Another exemplary embodiment of the water treatment compositioncomprises guar and polyaluminum sulfate.

Another exemplary embodiment of the water treatment compositioncomprises guar and polyaluminum silicate chloride.

Another exemplary embodiment of the water treatment compositioncomprises guar and polyaluminum silicate sulfate.

Another embodiment of the water treatment composition comprisesfree-flowing solid granules or powders of a water-soluble naturalnon-chemically derivatized polysaccharide(s) derived from a plant,microbe or animal that is admixed together with a free-flowing solid ofaluminum sulfate (alum), polyaluminum chloride, aluminum chlorohydrate,polyaluminum silicate sulfate, polyaluminum silicate chloride,polyaluminum sulfate, sodium aluminate, or polyaluminum chlorohydrategranules and/or powders.

The water treatment composition can also contain a preservative toprevent the growth of microorganisms including bacteria, fungi and/oryeast. Preservatives can include, but are not limited to, sodiumbenzoate, potassium sorbate, parabins, sorbic acid, and benzoic acid.

The polysaccharide(s) that comprise the water treatment composition caninclude combinations of the following natural non-derivatizedpolysaccharides: galactomannans; glucomannans; α-D glucans; xyloglucans;arabinoxylans; inulins; linear polysaccharides of alternatingα-(1-3)-and α-(1-4) galactopyranose units; linear polysaccharides ofglycosidically linked units of α-D-glucopyranose; linear polysaccharidesof glycosidically linked units of α-D-glucopyranose; heteropolymers ofglycosidically linked units of bothα-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan.

The water treatment composition can be comprised of a commerciallyeffective water-clarifying combination of natural non-derivatizedpolysaccharides and contain either polyaluminum chloride, aluminumchlorohydrate, polyaluminum chlorohydrate, aluminum sulfate, sodiumaluminate, polyaluminum sulfate, polyaluminum silicate chloride,polyaluminum silicate sulfate, or combinations thereof.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of polyaluminumchloride and a polysaccharide(s) or a combination of polysaccharidesselected from the following natural non-derivatized polysaccharides:galactomannans; glucomannans; α-D glucans; xyloglucans; arabinoxylans;inulins; linear polysaccharides of alternating α-(1-3)-and α-(1-4)galactopyranose units; linear polysaccharides of glycosidically linkedunits of α-D-glucopyranose; linear polysaccharides of glycosidicallylinked units of α-D-glucopyranose; heteropolymers of glycosidicallylinked units of both α-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or and aminoacid homopolymers, such aspolyglutamic acid, may be used.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of aluminumchlorohydrate and a polysaccharide(s) or a combination ofpolysaccharides selected from the following natural non-derivatizedpolysaccharides: galactomannans; glucomannans; α-D glucans; xyloglucans;arabinoxylans; inulins; linear polysaccharides of alternatingα-(1-3)-and α-(1-4) galactopyranose units; linear polysaccharides ofglycosidically linked units of α-D-glucopyranose; linear polysaccharidesof glycosidically linked units of α-D-glucopyranose; heteropolymers ofglycosidically linked units of bothα-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used. Another embodiment of a water treatment compositionis comprised of a commercially effective water-clarifying combination ofpolyaluminum chlorohydrate and a polysaccharide(s) or a combination ofpolysaccharides selected from the following natural non-derivatizedpolysaccharides: galactomannans; glucomannans; α-D glucans; xyloglucans;arabinoxylans; inulins; linear polysaccharides of alternatingα-(1-3)-and α-(1-4) galactopyranose units; linear polysaccharides ofglycosidically linked units of α-D-glucopyranose; linear polysaccharidesof glycosidically linked units of α-D-glucopyranose; heteropolymers ofglycosidically linked units of bothα-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of aluminum sulfateand a polysaccharide(s) or a combination of polysaccharides selectedfrom the following natural non-derivatized polysaccharides:galactomannans; glucomannans; α-D glucans; xyloglucans; arabinoxylans;inulins; linear polysaccharides of alternating α-(1-3)-and α-(1-4)galactopyranose units; linear polysaccharides of glycosidically linkedunits of α-D-glucopyranose; linear polysaccharides of glycosidicallylinked units of α-D-glucopyranose; heteropolymers of glycosidicallylinked units of both α-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of sodium aluminateand a polysaccharide(s) or a combination of polysaccharides selectedfrom the following natural non-derivatized polysaccharides:galactomannans; glucomannans; α-D glucans; xyloglucans; arabinoxylans;inulins; linear polysaccharides of alternating α-(1-3)-and α-(1-4)galactopyranose units; linear polysaccharides of glycosidically linkedunits of α-D-glucopyranose; linear polysaccharides of glycosidicallylinked units of α-D-glucopyranose; heteropolymers of glycosidicallylinked units of both α-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of polyaluminumsulfate and a polysaccharide(s) or a combination of polysaccharidesselected from the following natural non-derivatized polysaccharides:galactomannans; glucomannans; α-D glucans; xyloglucans; arabinoxylans;inulins; linear polysaccharides of alternating α-(1-3)-and α-(1-4)galactopyranose units; linear polysaccharides of glycosidically linkedunits of α-D-glucopyranose; linear polysaccharides of glycosidicallylinked units of α-D-glucopyranose; heteropolymers of glycosidicallylinked units of both α-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of polyaluminumsilicate chloride and a polysaccharide(s) or a combination ofpolysaccharides selected from the following natural non-derivatizedpolysaccharides: galactomannans; glucomannans; α-D glucans; xyloglucans;arabinoxylans; inulins; linear polysaccharides of alternatingα-(1-3)-and α-(1-4) galactopyranose units; linear polysaccharides ofglycosidically linked units of α-D-glucopyranose; linear polysaccharidesof glycosidically linked units of α-D-glucopyranose; heteropolymers ofglycosidically linked units of bothα-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of polyaluminumsilicate sulfate and a polysaccharide(s) or a combination ofpolysaccharides selected from the following natural non-derivatizedpolysaccharides: galactomannans; glucomannans; α-D glucans; xyloglucans;arabinoxylans; inulins; linear polysaccharides of alternatingα-(1-3)-and α-(1-4) galactopyranose units; linear polysaccharides ofglycosidically linked units of α-D-glucopyranose; linear polysaccharidesof glycosidically linked units of α-D-glucopyranose; heteropolymers ofglycosidically linked units of bothα-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used.

Another embodiment of a water treatment composition/formulation iscomprised of a commercially effective water-clarifying combination ofany two or more of polyaluminum chloride, aluminum chlorohydrate,polyaluminum chlorohydrate, sodium aluminate, polyaluminum sulfate,polyaluminum silicate chloride, polyaluminum silicate sulfate, andaluminum sulfate, or a combination of all aluminum compounds and apolysaccharide or a combination of polysaccharides selected from thefollowing natural non-derivatized polysaccharides: galactomannans;glucomannans; α-D glucans; xyloglucans; arabinoxylans; inulins; linearpolysaccharides of alternating α-(1-3)-and α-(1-4) galactopyranoseunits; linear polysaccharides of glycosidically linked units ofα-D-glucopyranose; linear polysaccharides of glycosidically linked unitsof α-D-glucopyranose; heteropolymers of glycosidically linked units ofboth α-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan. Additionallyor alternatively, the milk-derived protein sodium caseinate and/orhydrolyzed casein and/or aminoacid homopolymers, such as polyglutamicacid, may be used.

Another embodiment of a water treatment composition is comprised of acommercially effective water-clarifying combination of polyaluminumchloride, aluminum chlorohydrate, polyaluminum chlorohydrate, aluminumsulfate, sodium aluminate, polyaluminum sulfate, polyaluminum silicatechloride, polyaluminum silicate sulfate and a polysaccharide or acombination of polysaccharides selected from the following naturalnon-derivatized polysaccharides: galactomannans; glucomannans; α-Dglucans; xyloglucans; arabinoxylans; inulins; linear polysaccharides ofalternating α-(1-3)-and α-(1-4) galactopyranose units; linearpolysaccharides of glycosidically linked units of α-D-glucopyranose;linear polysaccharides of glycosidically linked units ofα-D-glucopyranose; heteropolymers of glycosidically linked units of bothα-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose.

Representative examples, although not exhaustive, include guar andlocust bean gums, gum arabic, gum tragacanth, starches (branched andlinear), agars, carrageenans, pectins, xanthan, konjac, cellulose,chitin, and chitosan.

Another embodiment of a water treatment composition comprises aguar-aluminum complex created by mixing a solution of polyaluminumchloride with an aqueous solution of dissolved guar. The compositionsolution is approximately 50% (wt/wt.) of polyaluminum chloride solution(for example, Kemira PAX-XL8 or PAX-XL6) and 50% (wt./wt.) of a 1%(wt./wt.) guar (for example, Guar Gum 50, FCC grade from Univar).Another embodiment of a water treatment composition comprises aguar-aluminum complex created by slowly adding 100 g of polyaluminumchloride (for example, Kemira PAX-XL6, 10.3% Al₂O₃), to 250 g aqueous 1%guar (for example, Univar 50) while mixing followed by adding 150 g ofaqueous alum (for example, Univar 48% aluminum sulfate). The compositionsolution is approximately 20% (wt/wt.) of polyaluminum chloride solutionand 50% (wt./wt.) of a 1% guar solution and 30% (wt./wt.) of a 48%aluminum sulfate solution.

Another embodiment of a water treatment composition comprises a guaraluminum complex created by mixing a solution of aluminum sulfate withsolid water-soluble guar. The composition is approximately 24% (wt./wt.)aluminum sulfate and 0.5% (wt./wt.) guar (for example, Univar guar gum50 lot 10202008).

In some embodiments, a method for clarifying and reducing the turbidityof water by treating the water with a water treatment compositioncomprised of guar and polyaluminum chloride, aluminum chlorohydrate,polyaluminum chlorohydrate, aluminum sulfate, sodium aluminate,polyaluminum sulfate, polyaluminum silicate chloride, polyaluminumsilicate sulfate or a combination thereof so as to cause theagglomeration and subsequent removal of shear-stable insoluble suspendedand/or partially water-soluble flocs and aggregates by collection on orwithin a filter media that allows easier more efficient backwashing andimproved prolonged use of said filter media. The method comprises addingan effective amount of the water treatment composition to the watercontaining insoluble suspended and/or partially water soluble dissolvedmaterial and allowing the water treatment composition to interact withthe suspended insoluble or soluble matter in order to allow the matterto agglomerate and settle under gravity and/or float to the surface. Theagglomerated matter can be separated from the water by any of a numberof means known in the art such as filtration, gravity settling,centrifugation, cyclone separator, vacuum filtration, or by flotationand skimming.

The filter media can include sand, diatomaceous earth, zeolite, carbon,non-woven or woven geotextile bags, filter cartridge bags, rope filters,woven or non-woven polypropylene or polyethylene mesh, cellulosicfabrics, metal or stainless steel screens.

The suspended insoluble matter can include the following: microorganismssuch as bacteria, viruses, protozoans (Cryptosporidium or Giardiaoocysts); proteins, oils, fats, algae, organic matter includinghydrocarbons and insoluble starches; pharmaceutical ingredients such asmaterials used to prepare vaccines; nutraceuticals; commercially usefulindustrial fibers; suspended sludge materials from municipal andindustrial wastewater; dredging solids; suspended materials from minetailings; suspended metal oxides, or metal oxide hydroxides, graphiteparticles; carbon particles; suspended materials from oil and gasdrilling and/or hydraulic fracturing operations; suspended matter inrecreational or water derived from aquaculture operations or aquariums;suspended matter present in construction runoff; and suspended matterpresent in water from oil refinery operations.

When the water treatment composition containing polyaluminum chlorideand guar is added to an aqueous body containing insoluble suspendedand/or partially water-soluble material, enhanced flocculationefficiency is observed that is synergistic compared to the flocculationefficiency observed from adding either polyaluminum chloride or guaralone when used at an equal dose.

Another embodiment is a method for removing a phosphate-containingcompound, such as orthophosphate, from water comprising adding a watertreatment composition containing guar and polyaluminum chloride,aluminum chlorohydrate, polyaluminum chlorohydrate, aluminum sulfate,sodium aluminate, polyaluminum sulfate, polyaluminum silicate chloride,polyaluminum silicate sulfate or a combination thereof tophosphate-containing water to remove or reduce the phosphateconcentration more than can be removed by either guar or polyaluminumchloride or alum alone when used at the same dose. The phosphate can beremoved by filtration or gravity settling.

DESCRIPTION OF THE DRAWINGS

The foregoing aspects and many of the attendant advantages of thisinvention will become more readily appreciated as the same become betterunderstood by reference to the following detailed description, whentaken in conjunction with the accompanying FIGURES:

FIG. 1 is a graph illustrating results of turbidity reduction using guarand various samples of polyaluminum chloride; and

FIG. 2 is a graph illustrating results of turbidity reduction using guarwith polyaluminum chloride and guar with alum.

DETAILED DESCRIPTION

Removal of suspended particulate or soluble matter in aqueous fluids canbe accomplished by coagulation and flocculation followed by settling,skimming, filtration, centrifugation or any combination thereof.Coagulation often involves the use of multivalent inorganic metal saltssuch as aluminum sulfate (alum), aluminum chloride, polyaluminumchloride, aluminum chlorohydrate, polyaluminum chlorohydrate, ironsulfate, or iron chloride.

Flocculants such as chitosan or polyacrylamides have also been usedseparately or in combination with alum or polyaluminum chloride to treatwater for reducing turbidity and/or removing suspended solid matter.Although the combination may offer improved coagulation, flocculationand floc size, the resulting floccules may still exhibit low shearstrength and come apart when subjected to low to moderate pressure oragitation. Improved backwashing of filters containing flocculatedinsoluble materials that do not cling to the filter media but releaseeasily from the filter media during backwashing cycles would be ofsignificant value. The use of a natural non-charged polysaccharide, suchas guar, in combination with an aluminum-containing coagulant, such aspolyaluminum chloride or aluminum chlorohydrate or polyaluminumchlorohydrate or aluminum sulfate or sodium aluminate or polyaluminumsulfate or polyaluminum silicate chloride or polyaluminum silicatesulfate, or some combination thereof may allow for easy and moreefficient backwashing. Other natural non-charged polysaccharides mayinclude locust bean gum, starch, konjac, and cellulose.

The water treatment composition used in the methods for clarifyingwater, reducing the turbidity of water, and removing phosphate fromwater includes an aluminum-containing coagulant or a combination ofaluminum-containing coagulants, and a natural non-charged polysaccharideor combination of natural non-charged polysaccharides. Optionally, thewater treatment composition may include water. The water treatmentcomposition may be applied as a solution or in a dry solid form. Thealuminum-containing coagulant, and the natural non-chargedpolysaccharide may be applied together in solution, or in dry solidform, or in a complexed form. The aluminum-containing coagulant, and thenatural non-charged polysaccharide may be applied separately, each beingin a solution or in a dry solid form. The aluminum-containing coagulantsand the natural non-charged polysaccharides are described further below.

Aluminum-Containing Coagulants

The aluminum-containing coagulants are readily commercially available.The aluminum-containing compounds may be applied as aqueous solutions orin a dry (solid) powder or granular form. The following may be usedsingly or in combination: polyaluminum chloride, aluminum chlorohydrate,polyaluminum chlorohydrate, aluminum sulfate, sodium aluminate,polyaluminum sulfate, polyaluminum silicate chloride, polyaluminumsilicate sulfate.

Aluminum sulfate has the formula, Al₂(SO₄)₃.xH₂O, wherein X is reportedto be 13, 14, 15, 16, 17, or 18, or a combination. Solutions can bedefined by the aluminum content or expressed in terms of equivalentalumina Al₂O₃.

Polyaluminum chloride may have the formula Al_(n)(OH)_(m)Cl_((3n-m)),wherein 0<m≦3n, and n≧1. See U.S. Pat. No.7,846,318, incorporated hereinexpressly by reference. The species can form polymers in water. The phcorrelates to the formula m/(3n). The higher the basicity of acoagulant, the lower the alkalinity consumption and, therefore, the lessthe pH of the water is reduced. Basicity can range from about 15% toabout 83% w/w in commercially available polyaluminum chlorides. Basicitycan be low, medium, or high basicity. Basicity can range from about 10%to about 83%, and any range derivable therebetween, such as between anyrange beginning from 10%, 20%, 30%, 40%, 50%, 60%, or 70%, and ending at20%, 30%, 40%, 50% ,60%, 70, or 80%.

Some polyaluminum chorides may have sulfate. In the literature, thesecompounds are also sometimes referred to as polyaluminum chlorides, andsometimes as polyaluminum chorosulfates. The formula of somepolyaluminum chlorides (polyaluminum chorosulfates) may beAl_(n)OH_(m)(SO₄)_(k)Cl_((3n-m-k)). Sulfate can range about 2% to 3% byweight.

Aluminum chlorohydrate is the name of the polyaluminum chloride wheren=2, and m=5. Aluminum chlorohydrate may have the formula Al₂Cl(OH)₅,which has a basicity of about 83%.

Suitable aluminum-containing coagulants are available from KemiraChemicals, Inc. under the designation PAX.

Polysaccharides

The polysaccharide(s) that comprise the water treatment composition caninclude combinations of the following natural non-derivatizedpolysaccharides: galactomannans; glucomannans; α-D glucans; xyloglucans;arabinoxylans; inulins; linear polysaccharides of alternatingα-(1-3)-and α-(1-4) galactopyranose units; linear polysaccharides ofglycosidically linked units of α-D-glucopyranose; linear polysaccharidesof glycosidically linked units of cc-D-glucopyranose; heteropolymers ofglycosidically linked units of bothα-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose. Representative examples,although not exhaustive, include guar and locust bean gums, gum arabic,gum tragacanth, starches (branched and linear), agars, carrageenans,pectins, xanthan, konjac, cellulose, chitin, and chitosan.

A natural non-charged polysaccharide includes guar. Guar (guar gum) is astraight chain galactomannan with galactose on every other mannose unit.Beta 1-4 glycosidic linkages couple the mannose units and the galactoseside chains are linked by alpha 1-6. A suitable guar gum for use isavailable from Univar, Inc. Other natural non-charged polysaccharidesmay include locust bean gum, starch, konjac, and cellulose.

Some embodiments of a method for clarifying water or removing phosphatefrom water include the steps: adding an aluminum-containing coagulantselected from polyaluminum chloride, aluminum chlorohydrate,polyaluminum chlorohydrate, aluminum sulfate, sodium aluminate,polyaluminum sulfate, polyaluminum silicate chloride, polyaluminumsilicate sulfate or a combination thereof, and a synergistic amount of anatural, non-charged polysaccharide to water containing matter; formingagglomerations in the water comprising the matter, thealuminum-containing compound, and the polysaccharide; and removing theagglomerations from the water to remove the matter from the water.

In some embodiments, the natural, non-charged polysaccharide is guar.

In some embodiments, adding the aluminum-containing coagulant andpolysaccharide comprises adding a solution of aluminum-containingcoagulant and guar.

In some embodiments, adding the aluminum-containing coagulant andpolysaccharide comprises adding solid forms of aluminum-containingcoagulant and guar.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight polyaluminum chloride.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight aluminum chlorohydrate.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight polyaluminum chlorohydrate.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight aluminum sulfate.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight sodium aluminate.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight polyaluminum sulfate.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight polyaluminum silicate chloride.

In some embodiments, the aluminum-containing coagulant is substantially100% by weight polyaluminum silicate sulfate.

In some embodiments, the aluminum-containing coagulant comprises asolution of polyaluminum chloride and water.

In some embodiments, the aluminum-containing coagulant comprises asolution of aluminum chlorohydrate and water.

In some embodiments, the aluminum-containing coagulant comprises asolution of polyaluminum chlorohydrate and water.

In some embodiments, the aluminum-containing coagulant comprises asolution of aluminum sulfate and water.

In some embodiments, the aluminum-containing coagulant comprises asolution of sodium aluminate and water.

In some embodiments, the aluminum-containing coagulant comprises asolution of polyaluminum sulfate and water.

In some embodiments, the aluminum-containing coagulant comprises asolution of polyaluminum silicate chloride and water.

In some embodiments, the aluminum-containing coagulant comprises asolution of polyaluminum silicate sulfate and water.

In some embodiments, the aluminum-containing coagulant is a solutionmade with the compound having the formula Al_(n)(OH)_(m)Cl_((3n-m)),wherein 0<m≦3n, and n≧1.

In some embodiments, the aluminum-containing coagulant is a solutionmade with the compound having the formula Al₂(SO₄)₃.xH₂O.

In some embodiments, the aluminum-containing coagulant is a solutionmade with the compound having the formula Al₂Cl(OH)₅.

In some embodiments, the ratio of polysaccharide to aluminum-containingcoagulant is about 1:34.

In some embodiments, the ratio of polysaccharide to aluminum-containingcoagulant is about 1:48.

In some embodiments, the ratio of polysaccharide to aluminum-containingcoagulant ranges from about 1:10 to about 1:100.

In some embodiments, the aluminum-containing coagulant and thepolysaccharide are added as a guar aluminum complex.

In some embodiments, the guar aluminum complex is made by the processcomprising adding solid guar to a solid aluminum-containing coagulantand adding water to the solid guar and aluminum-containing coagulant.

In some embodiments, the aluminum-containing compound and polysaccharideare added together.

In some embodiments, the aluminum-containing compound and polysaccharideare added separately.

In some embodiments, the phosphate that is removed is orthophosphate.

In some embodiments, the matter in the water includes microorganisms,bacteria, viruses, protozoans, Cryptosporidium oocysts, Giardia oocysts;proteins, oils, fats, algae, hydrocarbons, metal oxides, metal oxidehydroxides, insoluble starches; pharmaceuticals, nutraceuticals; fibers,polyaramids, dredging solids; suspended materials from mine tailings,graphite particles, carbon particles, suspended materials from oil orgas drilling or hydraulic fracturing; suspended matter in recreationalor water derived from aquaculture operations or aquariums; suspendedmatter present in construction runoff; and suspended matter present inwater from oil refinery operations.

In some embodiments, the polysaccharide is a natural non-chargedpolysaccharide selected from locust bean gum, starch, konjac, orcellulose.

Some embodiments of a method for clarifying water include the steps:adding an aluminum-containing coagulant selected from polyaluminumchloride, aluminum chlorohydrate, polyaluminum chlorohydrate, aluminumsulfate, sodium aluminate, polyaluminum sulfate, polyaluminum silicatechloride, polyaluminum silicate sulfate or a combination thereof, and asynergistic amount of a natural, non-charged polysaccharide to watercontaining a phosphate compound; forming agglomerations in the watercomprising the phosphate compound, the aluminum-containing coagulant,and the polysaccharide; and removing the agglomerations from the waterto remove the phosphate compound from the water.

In some embodiments, the phosphate compound is orthophosphate.

In some embodiments, the polysaccharide is guar.

In some embodiments, the aluminum-containing compound is polyaluminumchloride.

In some embodiments, the aluminum-containing compound is aluminumchlorohydrate.

In some embodiments, the aluminum-containing compound is polyaluminumchlorohydrate.

In some embodiments, the aluminum-containing compound is aluminumsulfate.

In some embodiments, the aluminum-containing compound is sodiumaluminate.

In some embodiments, the aluminum-containing compound is polyaluminumsulfate.

In some embodiments, the aluminum-containing compound is polyaluminumsilicate chloride.

In some embodiments, the aluminum-containing compound is polyaluminumsilicate sulfate.

In some embodiments, the ratio of polysaccharide to aluminum-containingcoagulant is about 1:34.

In some embodiments, the ratio of polysaccharide to aluminum-containingcoagulant is about 1:48.

In some embodiments, the ratio of polysaccharide to aluminum-containingcoagulant ranges from about 1:10 to about 1:100.

EXAMPLES Example 1

(Demonstration of Synergy of Guar and Aluminum Sulfate in TurbidityReduction)

1. Fill four glass scintillation (glass) vials each with 20-ml offlow-back/produced water

2. Mark one as “control”, cap and set aside

3. Add one or two drops of 1% by weight guar solution to two of thethree remaining vials, cap and shake.

4. Add 48% by weight aluminum sulfate/water solution using theequivalent number drops used in Step #3 to the third vial without guarand to one of the two vials treated with 1% guar solution, cap andshake.

5. Shake all four capped scintillation (glass) vials again and set asideat ambient T.

6. View flocculation and clarification performance.

TABLE 3 Initial alum/guar jar test key and results CONTENTS TREATMENT48% Alum 1% guar RESULTS Control NA NA No change 1 NA Yes No change 2Yes Yes Floc/Cleared 3 Yes NA No change

Results:

No observable flock or settling was observed in the produced watersamples treated with alum alone or guar alone. There was significantsettling observed in the sample treated with guar first followed byalum. There was no change in the untreated sample labeled “control”.

Discussion:

There appears to be a certain synergy present when alum and guar areused in combination. The sample treated with alum alone was unable toclear the sample and the same for the sample treated with guar alone.Only the sample containing both alum and guar produced a result.

Example 2

(Demonstration of Synergy of Guar and Aluminum Sulfate in PhosphateReduction)

Procedure

Orthophosphate-spiked water was prepared by adding 1.719 ml of phosphatestandard solution (from PAS-STM-8039 02 of phosphate procedure) to 1liter of deionized water. 100 ml of orthophosphate-spiked water wasdispensed into plastic sample cups.

1. Aluminum sulfate (48% by weight aluminum sulfate hydrate, 52% byweight water was used neat (undiluted).

2. Hybrid E—Guar aluminum complex created by mixing a solution ofaluminum sulfate with solid water-soluble guar. The composition isapproximately 24% (wt./wt.) alum and 0.5% (wt./wt.) guar (Univar guargum 50).

3. 100 microliters of either Aluminum sulfate or Hybrid E was added to100 ml of orthophosphate-spiked water which was mixed and allowed to sitfor various time periods. Controls received 100 microliters of wateralone. Following the various time periods, 12 ml of each treated watersample was filtered through a 0.45 micron filter, diluted 1:10 withdeionized water and reacted with 1 powder pillow of HACH reagent PhosVer3 and the phosphate concentration determined spectophotometrically usinga HACH spectrophotometer. In other experiments, the phosphateconcentration of the treated water was tested without filtration.

Results

As shown in Table 1, Alum and Hybrid E reduced the phosphateconcentration by 24% and 27% respectively compared to the non-treatedcontrol.

TABLE 1 Phosphate concentration of filtered treated water followingovernight incubation at room temperature Phosphate concentration inPhosphate treated water Concentration of corrected for 1:10 Treatment1:10 dilution (ppm) dilution (ppm) Percent Removal Control 1.29 12.9 0%Alum neat 0.98 9.8 24% Hybrid E 0.94 9.4 27%

100 microliters of either Alum, or Hybrid E was added to 100 ml oforthophosphate-spiked water contained in a 100 ml graduated cylinder andmixed. After sitting undisturbed for two hours at RT (room temperature),water was sampled from the top (100-90 ml), middle (50-40 ml) or bottom(20-10 ml) portion of each graduated cylinder. Sampled water was diluted1:10 with deionized water and tested without filtrationspectrophotometrically for phosphate concentration using powder pillowsof HACH PhosVer 3 reagent.

Results are shown in table 2 below.

TABLE 2 Phosphate concentration of treated water sampled at variouslevels in a graduated cylinder. Control phosphate water contained 10 ppmTop (100-90 ml) Middle (50-40 ml) Bottom (20-10 ml) Phosphate conc.Phosphate conc. Phosphate conc. Treatment (ppm) (ppm) (ppm) Alum 8.8 8.98.9 Hybrid E 8.1 8.3 8.0

Conclusion

Hybrid E appeared to reduce orthophosphate concentrations similar toalum using about half the amount of alum.

EXAMPLE 3

(Testing of Various PACs with Guar)

Product Testing Method:

1. 200 grams of Arizona Fine Dust ((PTI ID: 10943F) was mixed in 10liters of DI H2O to prepare the Arizona test dust solution.

2. 1N HC1 was added to the Arizona test dust solution to bring the pH to7.2 from a pH of 9.4.

3. 500mls of Arizona test dust solution was poured into separate 500 mlbottles and labeled respective to the guar/PAC formulation being added.

4. The respective guar/PAC formulation each containing a different PAC,was added to 500 ml of Arizona test dust solution to a finalconcentration of 50 ppm and mixed for approximately two minutes and thenallowed to settle for ten minutes (the concentration of guar andaluminum was the same for each formulation. Following ten minutes ofsettling, turbidity was measured for each Arizona test dust solutionthat was treated with the respective guar/PAC formulation. Controlnon-treated Arizona test dust solution exhibited a turbidity ofapproximately 8000 NTU. The results shown in FIG. 1 clearly demonstratethat formulation 29-RT exhibiting a basicity of 70% performedsignificantly better at reducing turbidity compared the formulations28RT and 30RT that exhibited a basicity of 75% and 51% respectively.Values represent the average of five replicates.

Description of the Samples:

240-48-28-RT

0.5 grams of guar (Univar, Lot # 10202008) was added to 17.22 grams ofGrade 28 PAC and stored as powder at room temperature on Dec. 20, 2012.After 4 weeks on 02/06/13, 82.28 grams of DI water was added, and mixedfor about 2 hours. The solution was then held and stored as liquid for27 days then tested. Grade 28 PAC has a basicity of 75% and an Al₂O₃content of 30.2%.

240-48-29-RT

0.5 grams of guar was added to 16.99 grams of Grade 29 PAC and stored aspowder at room temperature on Dec. 20, 2012. After 4 weeks on Feb. 06,2013, 82.51 grams of DI water was added, and mixed for about 2 hours.The solution was then held and stored as liquid for 27 days then tested.Grade 29 PAC has a basicity of 70% and an Al₂O₃ content of 30.6%.

240-48-30-RT Liquid

0.5 grams of guar was added to 16.99 grams of Grade 30 PAC and stored aspowder at room temperature on Dec. 20, 2012. After 4 weeks on Feb. 06,2013, 82.51 grams of DI water was added, and mixed for about 2 hours.The solution was then held and stored as liquid for 27 days then tested.Grade 30 PAC has a basicity of 51% and an Al₂O₃ content of 30.6%.

Results

FIG. 1 is an illustration of graph showing the results. Turbidity isreported in NTU. The sample 29@RT was the most effective in reducingturbidity. At 50 ppm, 29 @RT reduced turbidity to approximately 100 NTU,compared to approximately 300 NTU by 28@RT, and approximately 700 NTU by30@RT.

Example 4

A sample of frac pit water (sometimes referred to as drill water) fromBear Creek Services (Contly 27-H #1 34-H #1). The amount dosed was addedto 20 ml of sample, mixed, and then rested for 5 minutes before theturbidity was measured. The results are in the Table 3 below:

20 ml sample Control 1% Guar PAX-XL6 213-133-B Amount dosed 0 25 mg 25mg 50 mg NTU (5 min) 740 760 860 320

Formula 213-133-B is 50% by weight Kemira PAX-XL6 poly aluminum chloride(basicity 55%, Al₂O₃ 10.3%, Al 5.31%, Sulfate 2.5%), 50% by weight 1%guar solution in water (Univar 45 Guar). To make the product, the PAC isslowly added to guar solution while mixing, to get a uniform solution.

Example 5

(Testing of Guar/PAC vs. Guar/Alum)

Product Testing Method

1. 200 grams of Arizona Fine Dust ((PTI ID : 10943F) was mixed in 10liters of DI H2O to prepare the Arizona test dust solution.

2. 1N HCl was added to the Arizona test dust solution to bring the pH to7.2 from a pH of 9.4.

3. 500 mls of Arizona test dust solution was poured into separate 500 mlbottles.

4. The guar/PAC formulation and the guar/alum formulation was each addedto separate 500 ml aliquots of Arizona test dust solution to a finalconcentration of 50 ppm and then mixed for approximately two minutes andthen allowed to settle for ten minutes. The P-50 formulation is 50% byweight Kemira PAX-XL8 polyaluminum chloride (basicity ˜70%, Al₂O₃ 10%,Al 5.5%) and 50% by weight 1% guar solution in water. The A48formulation is the same as Hybrid E described earlier). Following tenminutes of settling, turbidity was measured for each Arizona test dustsolution that was treated with the respective guar/PAC formulation.Control non-treated Arizona test dust solution exhibited a turbidity ofapproximately 8000 NTU.

The results are shown in FIG. 2, wherein the values represent theaverage of five replicates. The results clearly demonstrate that theP-50 formulation performed significantly better at reducing turbiditycompared to the A48 (Hybrid E) formulation. Compare approximately 180NTUto 1000 NTU.

While illustrative embodiments have been illustrated and described, itwill be appreciated that various changes can be made therein withoutdeparting from the spirit and scope of the invention.

1-46. (canceled)
 47. A water treatment composition, comprising: analuminum-containing coagulant selected from polyaluminum chloride,aluminum chlorohydrate, polyaluminum chlorohydrate, aluminum sulfate,sodium aluminate, polyaluminum sulfate, polyaluminum silicate chloride,polyaluminum silicate sulfate, or a combination thereof, and a naturalnon-derivatized polysaccharide selected from guar, locust bean gum, gumarabic, gum tragacanth, starch (branched and linear), agar, carrageenan,pectin, xanthan, konjac, cellulose, chitin, a galactomannan,glucomannan, α-D glucan, xyloglucan, arabinoxylan, insulin, linearpolysaccharide of alternating α-(1-3)-and α-(1-4) galactopyranose units,linear polysaccharide of glycosidically linked units ofα-D-glucopyranose, linear polysaccharide of glycosidically linked unitsof α-D-glucopyranose, and heteropolymer of glycosidically linked unitsof both α-(1-4)-2-acetamido-2-deoxy-D-glucopyranose andα-(1-4)-2-amino-2-deoxy-D-glucopyranose, sodium caseinate, hydrolyzedcasein, an aminoacid homopolymer, or polyglutamic acid.
 48. The watertreatment composition of claim 47, wherein the polysaccharide is anon-charged polysaccharide.
 49. The water treatment composition of claim48, wherein the non-charged polysaccharide is selected from guar, locustbean gum, gum arabic, gum tragacanth, starch (branched and linear),agar, carrageenan, pectin, xanthan, konjac, or cellulose.
 50. The watertreatment composition of claim 47, wherein the composition is a solutioncomprising the aluminum-containing coagulant, polysaccharide, and water.51. The water treatment composition of claim 50, wherein the compositionis a solution comprising polyaluminum chloride, a polysaccharideselected from guar, locust bean gum, gum arabic, gum tragacanth, starch(branched and linear), agar, carrageenan, pectin, xanthan, konjac,cellulose, and water.
 52. The water treatment composition of claim 51,wherein the basicity of the polyaluminum chloride is between 10% toabout 83%.
 53. The water treatment composition of claim 47, wherein thealuminum-containing coagulant is a solution made with a compound havingthe formula Al_(n)(OH)_(m)Cl_((3n-m)),wherein 0<m≦3n, and n≧1.
 54. Thewater treatment composition of claim 47, which is a guar aluminumcomplex.
 55. The water treatment composition of claim 54, wherein theguar aluminum complex is made by the process selected from: (a) aprocess comprising adding solid guar and a solid aluminum-containingcoagulant and adding water to the solid guar and aluminum-containingcoagulant; (b) a process comprising adding solid guar and analuminum-containing coagulant solution and optionally adding water; or(c) a process comprising adding a solid aluminum-containing coagulantand a solution of guar and optionally adding water.
 56. A method forclarifying or reducing the turbidity of drill water, comprising: addingan aluminum-containing coagulant selected from polyaluminum chloride,aluminum chlorohydrate, polyaluminum chlorohydrate, aluminum sulfate,sodium aluminate, polyaluminum sulfate, polyaluminum silicate chloride,polyaluminum silicate sulfate or a combination thereof, and a natural,non-charged polysaccharide to water containing matter; formingagglomerations in the water comprising the matter, thealuminum-containing compound, and the polysaccharide; and removing theagglomerations from the water to remove the matter from the water. 57.The method of claim 56, wherein the natural, non-charged polysaccharideis guar, locust bean gum, starch, konjac, or cellulose.
 58. The methodof claim 56, comprising adding the water treatment composition of claim47 to the water.
 59. The method of claim 56, comprising (a) adding solidguar and a solid aluminum-containing coagulant and adding water to thesolid guar and aluminum-containing coagulant; (b) adding solid guar andan aluminum-containing coagulant solution and optionally adding water;or (c) adding a solid aluminum-containing coagulant and a solution ofguar and optionally adding water.
 60. The method of claim 56, whereinthe basicity of the aluminum-containing coagulant is between 10% toabout 83%.
 61. A method for clarifying or reducing the turbidity ofwater comprising hydrocarbons, comprising: adding an aluminum-containingcoagulant selected from polyaluminum chloride, aluminum chlorohydrate,polyaluminum chlorohydrate, aluminum sulfate, sodium aluminate,polyaluminum sulfate, polyaluminum silicate chloride, polyaluminumsilicate sulfate, or a combination thereof, and a natural, non-chargedpolysaccharide to water containing matter; forming agglomerations in thewater comprising the matter, the aluminum-containing compound, and thepolysaccharide; and removing the agglomerations from the water to removethe matter from the water.
 62. The method of claim 61, wherein thenatural, non-charged polysaccharide is guar, locust bean gum, starch,konjac, or cellulose.
 63. The method of claim 61, comprising adding thewater treatment composition of claim 47 to the water.
 64. The method ofclaim 61, comprising: (a) adding solid guar and a solidaluminum-containing coagulant and adding water to the solid guar andaluminum-containing coagulant; (b) adding solid guar and analuminum-containing coagulant solution and optionally adding water; or(c) adding a solid aluminum-containing coagulant and a solution of guarand optionally adding water.
 65. The method of claim 61, wherein thebasicity of the aluminum-containing coagulant is between 10% to about83%.
 66. A method for clarifying or reducing the turbidity of watercomprising suspended materials from oil or gas drilling or hydraulicfracturing or suspended matter present in water from oil refineryoperations, comprising: adding an aluminum-containing coagulant selectedfrom polyaluminum chloride, aluminum chlorohydrate, polyaluminumchlorohydrate, aluminum sulfate, sodium aluminate, polyaluminum sulfate,polyaluminum silicate chloride, polyaluminum silicate sulfate or acombination thereof, and a natural, non-charged polysaccharide to watercontaining matter; forming agglomerations in the water comprising thematter, the aluminum-containing compound, and the polysaccharide; andremoving the agglomerations from the water to remove the matter from thewater.
 67. The method of claim 66, wherein the natural, non-chargedpolysaccharide is guar, locust bean gum, starch, konjac, or cellulose.68. The method of claim 66, comprising adding the water treatmentcomposition of claim 47 to the water.
 69. The method of claim 66,comprising: (a) adding solid guar and a solid aluminum-containingcoagulant and adding water to the solid guar and aluminum-containingcoagulant; (b) adding solid guar and an aluminum-containing coagulantsolution and optionally adding water; or (c) adding a solidaluminum-containing coagulant and a solution of guar and optionallyadding water.
 70. The method of claim 66, wherein the basicity of thealuminum-containing coagulant is between 10% to about 83%.